ABSTRACT
Phenothiazinone is a promising yet underutilized fluorophore, possibly due to the lack of a general accessibility. This study reports a robust and scalable TEMPO-mediated electrochemical method to access a variety of phenothiazinones from 2-aminothiophenols and quinones. The electrosynthesis proceeds in a simple cell architecture under mild condition, and notably carbon-halogen bond in quinones remains compared to conventional methods, enabling orthogonal downstream functionalization. Mechanistic studies corroborate that TEMPO exerts a protective effect in avoiding product decomposition at the cathode. In particular, benzophenothiazinones show intriguing luminescence in both solid and solution state, and thus their photophysical properties are scrutinized in detail. Further bio-imaging of the lipid droplets in living cells highlights the considerable promise of benzophenothiazinones as fluorescent dye in the biomedical fields.
Subject(s)
Fluorescent Dyes , Luminescence , Fluorescent Dyes/chemistry , Carbon , Electrochemical Techniques , QuinonesABSTRACT
An efficient approach for the preparation of pyrazoles via a Pd(ii)/Cu(i)-catalyzed Sonogashira coupling/cyclization of N-propargyl sulfonylhydrazones has been established. In this study, we firstly report the strategic use of a Sonogashira reaction to construct pyrazole rings in a one step operation. With a broad range of functional group tolerance, bioactive 3-CF3 pyrazoles can also be synthesized easily through this domino coupling/cyclization sequence.
ABSTRACT
A series of pyridine-type ligands containing C≡C bonds were designed and synthesized for selective oxidative Heck reaction. These ligands were utilized as functional units and integrated into the skeleton of conjugated microporous polymers. 6,6'-diiodo-2,2'-bipyridine and 1,3,5-triethynylbenzene were polycondensed via Sonogashira cross-coupling strategy to afford CMP-1 material. The resultant CMP-1 was used as a heterogeneous catalytic ligand for the PdII-catalyzed oxidative Heck reaction with high linear selectivity. The linear selectivity of CMP-1 is about 30 times higher than that of bipyridine-based monomer ligand. This work opens a new front of using CMP as an intriguing platform for developing highly efficient catalysts in controlling the regioselectivity in organic reactions.
ABSTRACT
A highly efficient AgOTf catalyzed [3,3] sigmatropic rearrangement/1,3-H shift/6π aza-electrocyclization cascade reaction of N-propargylic hydrazones has been developed. This method provides a new mild synthetic route to various polysubstituted 1,6-dihydropyridazines including the 3-CF3-substituted ones with high selectivity.
ABSTRACT
An efficient gold-catalyzed cyclization/arylidene group transfer cascade reaction of N-propioloyl hydrazones has been developed. This method provides a novel approach for the synthesis of various functionalized 4-arylidenepyrazolones.
ABSTRACT
Hepatocellular carcinoma (HCC) is one of the most common malignancies worldwide with poor prognosis due to resistance to conventional chemotherapy and limited efficacy of radiotherapy. Previous studies have noted the induction of endoplasmic reticulum stress or apurinic endonuclease 1 (APE1) expression in many tumors. Therefore, the aim of this study was to investigate the relationship between endoplasmic reticulum (ER stress) and APE1 in hepatocellular carcinoma. Here we investigate the expression of APE1 during ER stress in HepG2 and Huh-7 cell lines. Tunicamycin or brefeldin A, two ER stress inducers, increased APE1 and GRP78, an ER stress marker, expression in HepG2 and Huh-7 cells. Induction of APE1 expression was observed through transcription level in response to ER stress. APE1 nuclear localization during ER stress was determined using immunofluorescence assays in HepG2 cells. Furthermore, expression of Hepatitis B virus pre-S2∆ large mutant surface protein (pre-S2∆), an ER stress-induced protein, also increased GRP78 and APE1 expression in the normal hepatocyte NeHepLxHT cell line. Similarly, tumor samples showed higher expression of APE1 in ER stress-correlated liver cancer tissue in vivo. Our results demonstrate that ER stress and HBV pre-S2∆ increased APE1 expression, which may play an important role in resistance to chemotherapeutic agents or tumor development. Therefore, these data provide an important chemotherapeutic strategy in ER stress and HBV pre-S2∆-associated tumors.
Subject(s)
DNA-(Apurinic or Apyrimidinic Site) Lyase/metabolism , Endoplasmic Reticulum Stress , Brefeldin A/pharmacology , DNA-(Apurinic or Apyrimidinic Site) Lyase/genetics , Endoplasmic Reticulum/drug effects , Endoplasmic Reticulum/metabolism , Endoplasmic Reticulum Chaperone BiP , Heat-Shock Proteins/metabolism , Hep G2 Cells , Hepatitis B Surface Antigens/genetics , Hepatitis B Surface Antigens/metabolism , Humans , Protein Precursors/genetics , Protein Precursors/metabolism , Tunicamycin/pharmacologyABSTRACT
Readily available NHC-Pd(II)-Mp complexes 2 showed efficient catalytic activity toward the Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids or potassium phenyltrifluoroborate, giving the expected coupling products in good to high yields. It should be noted that this is the first example so far of the phosphine-free, NHC-Pd(II) complexes catalyzed Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids.
ABSTRACT
A Co(acac)2 /POL-Xantphos@10PPh3 -catalyzed hydrosilylation of unsymmetrical internal alkynes with Ph2 SiH2 has been developed for the synthesis of highly selective syn-α-vinylsilane products. Furthermore, terminal alkynes were also used and gave the products with excellent regioselectivity and a wide functional group tolerance. Because this porous organic polymer combines the selectivity and activity merits of Xantphos with the stability advantage derived from the high concentration of PPh3 , the Co(acac)2 /POL-Xantphos@10PPh3 can be recycled multiple times without loss of activity and selectivity. This heterogeneous catalyst is expected to find promising applications in industrial synthesis.
ABSTRACT
A cobalt/POL-PPh3 catalyzed ( E)-selective hydrosilylation of alkynes with PhSiH3 has been developed for the synthesis of ( E)-ß-vinylsilanes with high regio- and stereoselectivity and wide functional group tolerance. It is the first report of using porous organic polymer as a recyclable regio- and stereoselective and efficient ligand in hydrosilylation reactions in which the polymer could be recycled numerous times in a continuous flow system without loss of activity and selectivity. The earth-abundant base-metal catalyst, coordinated by heterogeneous recyclable ligand, shows promise for industrial application.
ABSTRACT
A porous organic polymer (POL-Xantphos) was synthesized and employed as a heterogeneous ligand for selective hydrosilylation of alkynes. It exhibits high selectivity and catalytic efficiency toward a broad range of alkynes. Owing to the confinement effect of the micropore structure, POL-Xantphos was far superior to the monomeric Xantphos ligands in controlling the selectivity. By performing hydrosilylation in a flow reactor system, separation and regeneration of the Ni/POL-Xantphos catalyst are easily achieved without any loss in selectivity or activity.
ABSTRACT
Thiophenes containing an adjacent C≡C group as ligands for PdII-promoted organic reactions are reported for the first time. These ligands were utilized as catalytic sites and integrated into the skeleton of conjugated microporous polymers. By employing these CMP materials as selective regulators, oxidative Heck reactions between arylboronic esters and electronically unbiased alkenes provide highly selective linear products.
ABSTRACT
A novel method for the preparation of 5,6-dihydropyrazolo[5,1-a]isoquinoline via indium(III)-promoted halocyclizations of N-propargylic sulfonylhydrazones has been developed. The pyrazole and 3,4-dihydroisoquinoline moieties were synchronously formed via a cascade cyclization reaction using easily assembled open-chain compounds. The pyrazole and 3,4-dihydroisoquinoline moieties were formed via a cascade cyclization reaction using easily assembled open-chain compounds.
ABSTRACT
An efficient method for the preparation of 5,6-dihydropyrazolo[1,5-c]quinazolines via gold(I)-catalyzed chemoselective bicyclization of N-propargylic sulfonylhydrazones has been developed. This process relies on the chemoselective cyclization of the hydrazone nitrogen instead of the usually favored aniline nitrogen onto the alkyne. The synthetic utility of the current strategy is demonstrated through the synthesis of a potential Eg5/Kinesin spindle protein inhibitor.